US5487419A - Redispersible microdenominated cellulose - Google Patents

Redispersible microdenominated cellulose Download PDF

Info

Publication number
US5487419A
US5487419A US08/089,682 US8968293A US5487419A US 5487419 A US5487419 A US 5487419A US 8968293 A US8968293 A US 8968293A US 5487419 A US5487419 A US 5487419A
Authority
US
United States
Prior art keywords
cellulose
microdenominated
suspension
weight
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US08/089,682
Inventor
Michael K. Weibel
Original Assignee
Microcell Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Microcell Inc filed Critical Microcell Inc
Priority to US08/089,682 priority Critical patent/US5487419A/en
Priority to GB9500073A priority patent/GB2296725B/en
Priority to AU10029/95A priority patent/AU692803B2/en
Priority to FR9500097A priority patent/FR2729160B1/en
Priority to DE19500483A priority patent/DE19500483B4/en
Assigned to MICROCELL, INC. reassignment MICROCELL, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: WEIBEL, MICHEL K.
Application granted granted Critical
Publication of US5487419A publication Critical patent/US5487419A/en
Anticipated expiration legal-status Critical
Assigned to WEIBEL, MICHAEL reassignment WEIBEL, MICHAEL ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: PAUL, RICHARD S.
Assigned to WEIBEL, MICHAEL K., PAUL, RICHARD S. reassignment WEIBEL, MICHAEL K. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MICROCELL, INC.
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/16Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
    • D21H11/18Highly hydrated, swollen or fibrillatable fibres
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08BPOLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/02Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02Cellulose; Modified cellulose
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21CPRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/001Modification of pulp properties
    • D21C9/007Modification of pulp properties by mechanical or physical means
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08Cellulose derivatives
    • C08L1/26Cellulose ethers
    • C08L1/28Alkyl ethers
    • C08L1/286Alkyl ethers substituted with acid radicals, e.g. carboxymethyl cellulose [CMC]
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/02Starch; Degradation products thereof, e.g. dextrin

Definitions

  • This invention relates to redispersible microdenominated cellulose and to the production of microdenominated cellulose which may be dried and redispersed.
  • Microdenominated cellulose is produced from fibrous cellulosic material that has been extensively refined and converted into a dispersed tertiary level of structure, thereby achieving certain desirable properties attendant upon such structural change.
  • MDC is prepared by repeatedly passing a liquid suspension of fibrous cellulose through a zone of high shear, which is defined by two opposed surfaces, with one of the surfaces rotating relative to the other, under conditions and for a length of time sufficient to render the suspension substantially stable and to impart to the suspension a Canadian Standard Freeness that shows consistent increase with repeated passage of the cellulose suspension through the zone of high shear.
  • MDC The production of MDC can be efficiently carried out using standard refining equipment, e.g. a double disk refiner, operated in a way differing from the conventional use of this equipment in refining pulp for paper manufacture.
  • standard refining equipment e.g. a double disk refiner
  • the same equipment is used to achieve the opposite effect in preparing MDC, i.e., a high degree of disintegration of the fiber structure, which results in a cellulose product having very high surface area and high water absorbency.
  • the degree of disintegration is sufficiently severe that, as refining continues beyond that level normally used for paper manufacture (a Canadian Standard Freeness value approximating 100), a reversal of the Canadian Standard Freeness values occurs.
  • the process of this invention requires multiple passages of the pulp through the zone of high shear, which may typically involve ten to forty passages.
  • MDC microdenominated cellulose
  • MDC has a highly fibrillated structure resulting in a very high surface area and the ability to form stable gels.
  • Many of the uses contemplated for MDC in food, pharmaceutical, cosmetics, and the like are best served by providing MDC as a dried product that can be readily rehydrated and redispersed, whereby it exhibits properties approximating those of never dried MDC, i.e. MDC as discharged from the refiner or prior to drying. Unfortunately, this favorable structure and the desirable properties associated therewith are lost or greatly diminished upon drying the material.
  • additives are intended to prevent drying stress or hornification by inhibiting hydrogen bonding of the cellulose fibrils.
  • the additive forms hydrogen bonds or complexes with the cellulose fibrils and prevents them from bonding to each other during drying; thus, the cellulose fibrils remain readily accessible to water and easily rehydrated.
  • the additive must be capable of substantially inhibiting the hydrogen bonding between the fibrils of the cellulose.
  • the compounds found as useful additives are polyhydroxy compounds including particularly carbohydrates or carbohydrate-like compounds. These additive compounds must be used in substantial quantities, generally at least one half of the dried weight of the microfibrillated cellulose and preferably at least equal to microfibrillated cellulose weight in order to achieve the desired effect.
  • the foregoing and other objects of this invention are realized by a process of microdenominating cellulose in liquid suspension, drying the suspension of microdenominated cellulose in the presence of at least one dispersion agent which is believed to function by reducing or preventing bonding between the fibrils of cellulose.
  • the resultant product is a composition comprising the dry, microdenominated cellulose and the dispersion agent in an amount effective to impart to the cellulose a viscosity, when redispersed in water, that is at least fifty per cent of the viscosity of the equivalent concentration of never dried microdenominated cellulose.
  • the starting material for producing MDC is conveniently prepared by beating cellulosic sheet material in a hydrobeater in the presence of a suitable liquid, which disintegrates the sheet material and uniformly disperses the fibers in the liquid.
  • the exact amount of refining time required to produce MDC depends on the characteristics of the starting material e.g. the fiber length, the temperature of refining and the solids concentration in the pulp.
  • the length of processing is also influenced by the parameters of the shear zone in which the cellulose suspension is processed. In the case of a double disk refiner, these parameters include the amount of back pressure exerted on the cellulose suspension as it is subjected to shear stress during refining, the refiner plate surface configuration, the space between confronting refiner plates, refiner plate diameter and plate peripheral speed.
  • Efficiency is enhanced by operation at high pulp solids concentration, an elevated back pressure on the pulp during refining, elevated pulp temperatures coupled with maximum temperature control, adjustment of the gap between confronting refiner plates by keying on a pre-selected value of amperage to the refiner motor and a refiner plate configuration and peripheral speed that promotes "rubbing" or fraying rather than cutting.
  • refining proceeds most efficiently as the solids concentration in the pulp is increased, however, there is a limit to how high the solids concentration can be and still have the pulp flow through the system.
  • a short-fibered material like oat can be concentrated to almost twice the solids concentration possible with softwood and wheat, both long-fibered materials.
  • Preferred operating conditions for preparation of MDC in a double disk refiner are as follows: fiber length of about 50 to 3000 microns, or greater; refining temperature of about 60° F. to about 200° F.; a solids concentration of about 2 to about 10% by weight of the cellulose suspension; and back pressure of about 10 to about 40 psi.
  • a primary indicator used to monitor the extent of refining of the cellulosic material is the Canadian Standard Freeness value as measured using test equipment and procedures contained in TAPPI 227 "Freeness of Pulp” J. Casey, Pulp and Paper (1980). Freeness has been shown to be related to the surface conditions and the swelling of fiber which influences drainage. As refining continues beyond levels normally practiced in conventional paper making, the dimensions of the resulting structures become sufficiently small such that a reversal of freeness values occurs, i.e. increasing rather than diminishing values of freeness as refining continues. This anomalous rise of freeness is referred to herein as "false freeness". Once the reversal occurs and refining continues thereafter, the measured freeness value increases until a maximum value of approximately 800 is reached.
  • the refined material has been rendered sufficiently supple and fine (dimensionally small) that it readily passes through the perforations of the perforated plate of the tester along with the water.
  • the suspension behaves as though it were fiber-free water of the same total volume as the fiber-containing sample being measured. This is the limiting condition for obtaining meaningful data from freeness measurements.
  • the cellulose suspension achieves this desired level of freeness, it becomes substantially stable, which is intended to mean that there is no visible segregation of the continuous phase from the disperse phase, even upon standing for a reasonable period of time.
  • a parameter useful in the characterization and description of MDC is the settled volume of aqueous dispersions of differing solids content after twenty-four hours of settling.
  • the settled volume of a sample of MDC is determined by dispersing a known weight of cellulose (dry weight basis) in a known amount of water, e.g. in a graduated cylinder. After a prescribed settling time, the volume of the bed of suspended cellulose is measured with reference to the total volume of the continuous aqueous phase. The settled volume is expressed as a percentage of the bed volume to the total volume. From this data the solids concentration in an aqueous dispersion that results in a settled volume that is fifty percent of the original volume can be determined and used to characterize the product.
  • a characteristic of MDC is that a 1% by weight aqueous suspension has a settled volume greater than 50% after twenty-four hours.
  • Water retention is another parameter for characterizing MDC. Water retention values are determined by employing a pressure filtration apparatus (Baroid Model 301 for low pressure fluid loss control measurements, N. L. Baroid Corporation, Houston, Tex.) routinely used to evaluate drilling fluid properties. A 100 gram aliquot of a nominal 4 to 8% w/w aqueous dispersion of cellulose is loaded into the filter cell chamber, the cell chamber is capped and subjected to 30 psig. pressure from a regulated nitrogen source. The water discharged from the filtration cell chamber is collected and pressure continued for thirty seconds after observation of the first gas discharge. The nitrogen source is then turned off and collection of discharged water continued for one minute or until the gas discharge ceases, whichever event occurs first. Basically the technique employs pneumatic, pressure filtration to remove interstitial water from the particulate phase.
  • the expressed volume of water is recorded along with the weight of wet cake.
  • the wet cake is then dried for sixteen hours at 95 degrees Centigrade or until a constant weight is recorded.
  • the water retention value is computed as the ratio of (wet cake weight minus the dry cake weight) to (dry cake weight) times 100. This technique provides a good estimate of the capillary and absorptive retention of water by the cellulose solids by removing the interstitial water from the cake solids. The procedure is quick (5 to 10 minutes) and highly reproducible.
  • the water retention value of MDC is characteristically at least 350%, and preferably at least 500%.
  • Viscosity may also be used as a characterizing property of MDC.
  • Apparent viscosities of an aqueous dispersions of 1.5% w/w MDC solids samples were determined with a Brookfield Viscometer model DV-III using spindle SC4-16 with the small cell adapter at a number of shear conditions (5 through 100 RPM). The samples were pre-dispersed by high speed mixing for three minutes at 10,000 RPM with a rotor stator type mixer (Omni International, model 1000). The viscosities measured for final refined product (MDC) of the three examples are shown in Table 1.
  • the softwood fiber product exhibited a viscosity of approximately 8,000 centipoise at a spindle speed of 100 RPM.
  • the white wheat fiber product had a viscosity of approximately 6,000 and the oat fiber a viscosity of approximately 1,300 at the same measurement conditions as for the softwood fiber. It appears the wide range in the measured viscosities is primarily due to the differences in fibril length and other ultrastructural characteristics of the starting materials.
  • Viscosity measurements on MDC dispersions are made on a heterogeneous mixture (an interacting particle ensemble suspended in a fluid medium). Viscosity measurement is normally applied to homogenous systems. Because of the heterogeneous nature of the mixture a certain degree of mechanical distortion occurs in the mixture around the rotating spindle used to determine shear stress forces within the mixture. Consequently shear/shear stress measurements are time and history dependent. As such the measurement is not a true viscosity in the conventional sense but rather provides a reproducible measurement that has been found useful for characterizing the degree of microdenomination and in describing the implementation of this invention.
  • two substances have been found to produce a synergistic effect when used in combination as a dispersion agent in the practice of this invention.
  • the substances are maltodextrin and carboxymethylcellulose (CMC), which need only be added in modest quantities relative to the weight of the MDC.
  • the preferred amount of the maltodextrin is about one-half to one and one-half the weight of the MDC while the preferred amount of the CMC is about 5% to about 15% the weight of the MDC.
  • Maltodextrins are short chain oligiosaccharides reduced by the controlled hydrolysis of starch.
  • the degree of polymerization (DP) of maltodextrins is typically less than thirty and higher than five.
  • Commercial maltodextrins are excellent film formers and display low viscosity aqueous solutions at relatively high solids levels, typically 10 to 30%. They are readily available in food grades at reasonable cost.
  • CMC is a random ether substituted homopolymer of glucose produced by reaction of alkaline cellulose with chloroacetic acid. It also is food approved and readily available at relatively low cost. CMC has long been employed as a dispersant for cellulose slurries in the pulp and paper industry. It has been used as a drying additive for redispersion of microcrystalline cellulose and in drying of other, refined high surface area cellulose products. CMC (and other random substituted cellulose ethers) are believed to have regions of low to no substitution which have relatively high affinity for certain surface orientation of their particulate counterpart, the unsubstituted beta-glucan chain ensemble constituting refined cellulose.
  • maltodextrin and CMC act synergistically to keep the fibrils from bonding firmly together during drying have yet to be fully elucidated, it is believed to involve cooperative interaction, of sorts, between the two substances.
  • the maltodextrin is believed to provide a glass-like matrix that encases the cellulose fibrils while the CMC apparently binds to the fibril surfaces sufficiently to retard collapse to the point that enough water is removed to solidify the entrapping matrix.
  • the two substances in combination are very effective in prohibiting irreversible collapse of MDC during drying, thus allowing rapid dehydration and dispersement to occur and preserving to a substantial extent the favorable properties exhibited by never dried MDC.
  • the dispersion agent may optionally include lecithin in an amount from 0.1% to about 10% based on the weight of the MDC.
  • the white wheat fiber used in this example is a commercially available refined fiber product derived from bleached wheat chaff obtained from Watson Foods Company, West Haven Conn.
  • the white wheat product was obtained as a nominal 40% w/w nonvolatile solids fiber mat.
  • the product was stated to be 98% total dietary fiber by the Prosky method.
  • the refiner of this example is a twenty-eight inch diameter double disc unit powered by a 250 horsepower motor.
  • the refiner plates mounted on the discs are made of sharloy (a nickel hardened steel).
  • the refiner plates were not equipped with dams.
  • the faces of the particular refiner plates used in this refiner consists of alternate bars and grooves oriented so that bars of the adjacent refiner plates (one static and the other revolving) move relative to one another with a scissoring action occurring as the bars of each confronting plate move past one another.
  • the refiner plates on the revolving disc move at 713 revolutions per minute. Based on the outer periphery of the refiner disc extending to 13 and 1/4 inches from the centerline of the drive shaft, this corresponds to peripheral speed of about 4,900 feet per minute.
  • the pulp was continuously circulated at a rate of approximately 250 gallons per minute through the refiner and back to the holding tank. Passage of the cellulose suspension through the refiner occurs so as to have equal flow on each side of the revolving disc.
  • One disc of the refiner is fixed while the other is sliding. This allows the distance between adjacent discs to be adjusted.
  • discs In the full open position (typical of startup or shutdown), discs are one and three-quarters inch apart. During refining, the discs are of the order of one to two thousands of an inch apart. Rather than adjust the gap between discs to a specific spacing, the value of the amperage to the motor driving the refiner is used to establish spacing. The procedure upon startup is to move the discs from the full open position to a closer position where the amperage reading increases until it reaches 310 amps. At this point, maximum power is being delivered from the motor. Once this point is reached, the back pressure on the refiner is increased by closing down the valve on the line returning pulp from the refiner to the holding tank.
  • the back pressure is normally raised from an initial value of about 14 psig to a final value of about 35 psig.
  • the amperage drawn by the motor decreases to about 260 amps.
  • the sliding disc is adjusted to bring the discs closer together until the desired 310 amps are drawn by the motor. Once this is done, there is no further adjustment of the sliding disc unless the motor amperage drops significantly. This may occur as refining proceeds if certain properties of the pulp change significantly. In that event, the sliding disc is moved to reduce the gap between the discs until either the desired amperage is once again achieved, or the discs begin to squeal. Squealing is to be avoided as it is indicative of excessive disc wear and leads to high refiner plate replacement costs.
  • a gate-type mixer in the holding tank continuously mixed the contents during refining.
  • a back pressure of 34 pounds per square inch was maintained in the return line from the refiner outlet to the holding tank.
  • the recycle operation continued for approximately six hours during which the Canadian Standard Freeness of the pulp changed from an initial value of 190 to a final "false" value of 780 ml.
  • the temperature of the pulp increased from an initial value of 64 to a final value of 190 degrees Fahrenheit.
  • the amperage drawn by the 250 horsepower motor of the refiner varied from 310 initially to 290 amperes at completion of refining.
  • Energy input to the refiner was approximately 1.2 kilowatt-hours per pound of refined fiber processed (dry weight basis).
  • a typical high alpha-cellulose content cellulose from wheat was refined to a Canadian Standard Freeness of 790 according to the procedure described in Example 1, above, mixed with dispersion agent and dried in a 25 square foot Buflovak double drum dryer (two 24-inch diameter, 24-inch width drums).
  • the resultant mixture on a dry basis consisted of 56% w/w MDC, 39% w/w maltodextrin obtained from Staley, Decatur, IA (Lodex-15), 4% w/w carboxymethylcellulose type HP-5HS obtained from Dai-Ichikoyyo Seiyaku Company Ltd., Japan and 1% w/w soy lecithin obtained from Cargill, Decatur Ill.
  • This mixture was then fed as an aqueous dispersion of 4.55% total solids at a rate of 414 pounds per hour to a double drum dryer to produce a dried product of 93.3% solids.
  • the drums revolving at five revolutions per minute were heated by 100 psig steam.
  • the nip thickness on both drums was set at 0.01 inches. Dried product was removed as a thin continuous film from the drums and subsequently ground to flake and powdered products.
  • the 5 rpm viscosities of the dried flake and powdered products after drying and aqueous redispersion at the same solids content as the original dispersion with a Hamilton Beach Scovill Mixer model 936 ZSA at 2 minute (medium speed) were 3,410 and 3,095 centipoise, respectively.
  • the complete viscosity/shear profiles for these three aqueous dispersions are shown in Table 1.
  • the viscosity of the same powdered product after high shear redispersion for three minutes at 10,000 rpm with a Omni Digi-system rotostator type mixer (20 mm. generator) was 3,265 centipoise.
  • the belt speed was 59 feet per minute and the nip thickness at the applicator bar was set at 0.026 inches.
  • a sixty foot length of the belt was heated by 50 psig. steam. Dried product was removed as a thin continuous film and subsequently ground to flake and powdered products.

Abstract

A process for the production of and a composition of redispersible mechanically disassembled cellulose and the resultant product, referred to as microdenominated cellulose (MDC). The process is characterized by drying the MDC in the presence of a dispersion agent. The product is characterized by a settled volume of greater than 50%, as determined on the basis of a 1% by weight suspension in water after twenty-four hours, and a water retention value of over 350%. MDC is useful as an ingredient in foods, pharmaceutical and cosmetic products.

Description

This invention relates to redispersible microdenominated cellulose and to the production of microdenominated cellulose which may be dried and redispersed.
BACKGROUND OF THE INVENTION
Microdenominated cellulose (MDC) is produced from fibrous cellulosic material that has been extensively refined and converted into a dispersed tertiary level of structure, thereby achieving certain desirable properties attendant upon such structural change.
MDC is prepared by repeatedly passing a liquid suspension of fibrous cellulose through a zone of high shear, which is defined by two opposed surfaces, with one of the surfaces rotating relative to the other, under conditions and for a length of time sufficient to render the suspension substantially stable and to impart to the suspension a Canadian Standard Freeness that shows consistent increase with repeated passage of the cellulose suspension through the zone of high shear.
The production of MDC can be efficiently carried out using standard refining equipment, e.g. a double disk refiner, operated in a way differing from the conventional use of this equipment in refining pulp for paper manufacture. Whereas paper manufacture calls for minimum damage to the fiber during refining and a Canadian Standard Freeness consistent with good drainage of water from the pulp, the same equipment is used to achieve the opposite effect in preparing MDC, i.e., a high degree of disintegration of the fiber structure, which results in a cellulose product having very high surface area and high water absorbency. The degree of disintegration is sufficiently severe that, as refining continues beyond that level normally used for paper manufacture (a Canadian Standard Freeness value approximating 100), a reversal of the Canadian Standard Freeness values occurs. The reason for this reversal is that the dispersed fiber becomes sufficiently microdenominated that gradually greater amounts of fiber begin to pass through the perforated plate of the Canadian Standard Freeness tester with water, thus leading to a progressive increase in the measured value as refining continues. Continuation of refining ultimately results in essentially all of the refined fiber readily passing through the perforated plate with water. At this stage of processing, the measured Canadian Standard Freeness value is typical of that for unimpeded passage of water through the perforated plate of the test unit.
Whereas a single stage, and at most two stages are used for conventional refiner processing in paper manufacture, the process of this invention requires multiple passages of the pulp through the zone of high shear, which may typically involve ten to forty passages.
In paper manufacture beating or refining increases the area of contact between dispersed fibers by increasing the surface area through dispersion and fibrillation. MDC manufacture applies and extends such processing to a much greater degree. It is believed that the extent of refinement needed to achieve this high degree of fibrillation leads to a concomitant disassembly of tertiary structure, and perhaps even secondary structure. The result is an ultrastructurally dispersed form of cellulose with very high surface area.
The product of the invention, MDC, is characterized by a settled volume greater than about 50% after twenty-four hours, as based on 1% by weight aqueous suspension, and water retention greater than about 500%. Procedures for determining the settled volume and water retention values of MDC are described in detail below. Details regarding the preparation of microdenominated cellulose (MDC) are set forth in our copending U.S. patent application Ser. No. 08/089,683, filed Jul. 9, 1993 entitled "Process for Making Microdenominated Cellulose" in the names of Michael K. Weibel and Richard S. Paul, which is commonly owned and filed concurrently with the present application. The entire disclosure of the aforesaid related application is incorporated in the present specification by reference as if set forth herein in full. Because the extent to which it is refined, MDC has a highly fibrillated structure resulting in a very high surface area and the ability to form stable gels. Many of the uses contemplated for MDC in food, pharmaceutical, cosmetics, and the like are best served by providing MDC as a dried product that can be readily rehydrated and redispersed, whereby it exhibits properties approximating those of never dried MDC, i.e. MDC as discharged from the refiner or prior to drying. Unfortunately, this favorable structure and the desirable properties associated therewith are lost or greatly diminished upon drying the material. This occurs as a result of a partially irreversible collapse of the structure of the cellulose fibers due to shrinkage forces exerted during drying (hornification). The favorable dispersibility, hydration and viscosity properties of MDC are lost or substantially modified depending on the severity of drying.
A number of techniques have been developed heretofore to avoid or substantially lessen the adverse effects of drying on cellulose. They include, among others, the use of additives, solvent replacement of water and modified drying techniques. The latter two approaches are described in U.S. Pat. No. 3,023,104. Water can be displaced by a water miscible organic compound of low molecular weight such as methanol, ethanol, propanol, etc. followed by evaporation of the displacement fluid. Modified drying methods include spray drying in vacuum or air up to 100 to 105 degrees Centigrade, freeze drying and drum drying.
Most additives are intended to prevent drying stress or hornification by inhibiting hydrogen bonding of the cellulose fibrils. As disclosed in U.S. Pat. No. 4,481,076, the additive forms hydrogen bonds or complexes with the cellulose fibrils and prevents them from bonding to each other during drying; thus, the cellulose fibrils remain readily accessible to water and easily rehydrated. To perform this function the additive must be capable of substantially inhibiting the hydrogen bonding between the fibrils of the cellulose. Among the compounds found as useful additives are polyhydroxy compounds including particularly carbohydrates or carbohydrate-like compounds. These additive compounds must be used in substantial quantities, generally at least one half of the dried weight of the microfibrillated cellulose and preferably at least equal to microfibrillated cellulose weight in order to achieve the desired effect.
SUMMARY OF THE INVENTION
It is a primary object of this invention to provide dry microdenominated cellulose that can be readily redispersed in water and exhibit properties after redispersion that are essentially equivalent to those of never dried microdenominated cellulose.
The foregoing and other objects of this invention are realized by a process of microdenominating cellulose in liquid suspension, drying the suspension of microdenominated cellulose in the presence of at least one dispersion agent which is believed to function by reducing or preventing bonding between the fibrils of cellulose. The resultant product is a composition comprising the dry, microdenominated cellulose and the dispersion agent in an amount effective to impart to the cellulose a viscosity, when redispersed in water, that is at least fifty per cent of the viscosity of the equivalent concentration of never dried microdenominated cellulose.
DETAILED DESCRIPTION OF THE INVENTION
The starting material for producing MDC is conveniently prepared by beating cellulosic sheet material in a hydrobeater in the presence of a suitable liquid, which disintegrates the sheet material and uniformly disperses the fibers in the liquid.
The exact amount of refining time required to produce MDC depends on the characteristics of the starting material e.g. the fiber length, the temperature of refining and the solids concentration in the pulp. The length of processing is also influenced by the parameters of the shear zone in which the cellulose suspension is processed. In the case of a double disk refiner, these parameters include the amount of back pressure exerted on the cellulose suspension as it is subjected to shear stress during refining, the refiner plate surface configuration, the space between confronting refiner plates, refiner plate diameter and plate peripheral speed. Efficiency is enhanced by operation at high pulp solids concentration, an elevated back pressure on the pulp during refining, elevated pulp temperatures coupled with maximum temperature control, adjustment of the gap between confronting refiner plates by keying on a pre-selected value of amperage to the refiner motor and a refiner plate configuration and peripheral speed that promotes "rubbing" or fraying rather than cutting. Although refining proceeds most efficiently as the solids concentration in the pulp is increased, however, there is a limit to how high the solids concentration can be and still have the pulp flow through the system. A short-fibered material like oat can be concentrated to almost twice the solids concentration possible with softwood and wheat, both long-fibered materials.
Preferred operating conditions for preparation of MDC in a double disk refiner are as follows: fiber length of about 50 to 3000 microns, or greater; refining temperature of about 60° F. to about 200° F.; a solids concentration of about 2 to about 10% by weight of the cellulose suspension; and back pressure of about 10 to about 40 psi.
The remaining parameters, including plate configurations, spacing between adjacent plates, plate diameter and peripheral plate speed will depend on the particular model of refiner selected to process the MDC. A typical run employing a Black Clawson 28-inch Twin Hydradisc refiner is exemplified below.
A primary indicator used to monitor the extent of refining of the cellulosic material is the Canadian Standard Freeness value as measured using test equipment and procedures contained in TAPPI 227 "Freeness of Pulp" J. Casey, Pulp and Paper (1980). Freeness has been shown to be related to the surface conditions and the swelling of fiber which influences drainage. As refining continues beyond levels normally practiced in conventional paper making, the dimensions of the resulting structures become sufficiently small such that a reversal of freeness values occurs, i.e. increasing rather than diminishing values of freeness as refining continues. This anomalous rise of freeness is referred to herein as "false freeness". Once the reversal occurs and refining continues thereafter, the measured freeness value increases until a maximum value of approximately 800 is reached. At this point the refined material has been rendered sufficiently supple and fine (dimensionally small) that it readily passes through the perforations of the perforated plate of the tester along with the water. In other words, the suspension behaves as though it were fiber-free water of the same total volume as the fiber-containing sample being measured. This is the limiting condition for obtaining meaningful data from freeness measurements. As the cellulose suspension achieves this desired level of freeness, it becomes substantially stable, which is intended to mean that there is no visible segregation of the continuous phase from the disperse phase, even upon standing for a reasonable period of time.
Several other parameters or properties, in addition to Canadian Standard Freeness, serve to characterize MDC.
A parameter useful in the characterization and description of MDC is the settled volume of aqueous dispersions of differing solids content after twenty-four hours of settling. The settled volume of a sample of MDC is determined by dispersing a known weight of cellulose (dry weight basis) in a known amount of water, e.g. in a graduated cylinder. After a prescribed settling time, the volume of the bed of suspended cellulose is measured with reference to the total volume of the continuous aqueous phase. The settled volume is expressed as a percentage of the bed volume to the total volume. From this data the solids concentration in an aqueous dispersion that results in a settled volume that is fifty percent of the original volume can be determined and used to characterize the product. A characteristic of MDC is that a 1% by weight aqueous suspension has a settled volume greater than 50% after twenty-four hours.
Water retention is another parameter for characterizing MDC. Water retention values are determined by employing a pressure filtration apparatus (Baroid Model 301 for low pressure fluid loss control measurements, N. L. Baroid Corporation, Houston, Tex.) routinely used to evaluate drilling fluid properties. A 100 gram aliquot of a nominal 4 to 8% w/w aqueous dispersion of cellulose is loaded into the filter cell chamber, the cell chamber is capped and subjected to 30 psig. pressure from a regulated nitrogen source. The water discharged from the filtration cell chamber is collected and pressure continued for thirty seconds after observation of the first gas discharge. The nitrogen source is then turned off and collection of discharged water continued for one minute or until the gas discharge ceases, whichever event occurs first. Basically the technique employs pneumatic, pressure filtration to remove interstitial water from the particulate phase.
The expressed volume of water is recorded along with the weight of wet cake. The wet cake is then dried for sixteen hours at 95 degrees Centigrade or until a constant weight is recorded. The water retention value is computed as the ratio of (wet cake weight minus the dry cake weight) to (dry cake weight) times 100. This technique provides a good estimate of the capillary and absorptive retention of water by the cellulose solids by removing the interstitial water from the cake solids. The procedure is quick (5 to 10 minutes) and highly reproducible. The water retention value of MDC is characteristically at least 350%, and preferably at least 500%.
Viscosity may also be used as a characterizing property of MDC. Apparent viscosities of an aqueous dispersions of 1.5% w/w MDC solids samples were determined with a Brookfield Viscometer model DV-III using spindle SC4-16 with the small cell adapter at a number of shear conditions (5 through 100 RPM). The samples were pre-dispersed by high speed mixing for three minutes at 10,000 RPM with a rotor stator type mixer (Omni International, model 1000). The viscosities measured for final refined product (MDC) of the three examples are shown in Table 1. The softwood fiber product exhibited a viscosity of approximately 8,000 centipoise at a spindle speed of 100 RPM. The white wheat fiber product had a viscosity of approximately 6,000 and the oat fiber a viscosity of approximately 1,300 at the same measurement conditions as for the softwood fiber. It appears the wide range in the measured viscosities is primarily due to the differences in fibril length and other ultrastructural characteristics of the starting materials.
It should be understood that the above viscosity measurements on MDC dispersions are made on a heterogeneous mixture (an interacting particle ensemble suspended in a fluid medium). Viscosity measurement is normally applied to homogenous systems. Because of the heterogeneous nature of the mixture a certain degree of mechanical distortion occurs in the mixture around the rotating spindle used to determine shear stress forces within the mixture. Consequently shear/shear stress measurements are time and history dependent. As such the measurement is not a true viscosity in the conventional sense but rather provides a reproducible measurement that has been found useful for characterizing the degree of microdenomination and in describing the implementation of this invention.
According to a preferred embodiment, two substances have been found to produce a synergistic effect when used in combination as a dispersion agent in the practice of this invention. The substances are maltodextrin and carboxymethylcellulose (CMC), which need only be added in modest quantities relative to the weight of the MDC. The preferred amount of the maltodextrin is about one-half to one and one-half the weight of the MDC while the preferred amount of the CMC is about 5% to about 15% the weight of the MDC.
Maltodextrins are short chain oligiosaccharides reduced by the controlled hydrolysis of starch. The degree of polymerization (DP) of maltodextrins is typically less than thirty and higher than five. Commercial maltodextrins are excellent film formers and display low viscosity aqueous solutions at relatively high solids levels, typically 10 to 30%. They are readily available in food grades at reasonable cost.
CMC is a random ether substituted homopolymer of glucose produced by reaction of alkaline cellulose with chloroacetic acid. It also is food approved and readily available at relatively low cost. CMC has long been employed as a dispersant for cellulose slurries in the pulp and paper industry. It has been used as a drying additive for redispersion of microcrystalline cellulose and in drying of other, refined high surface area cellulose products. CMC (and other random substituted cellulose ethers) are believed to have regions of low to no substitution which have relatively high affinity for certain surface orientation of their particulate counterpart, the unsubstituted beta-glucan chain ensemble constituting refined cellulose. In the case of CMC for which each carboxymethyl substituent bears a stationary negative charge at a pH greater than 3.5, the binding of this substituted oligiosaccharide to a cellulosic surface would impart substantial stationary charge and negative zeta potential. Although not intending to be bound by any particular mechanism of operation, it is believed that such surface potential tends to retard collapse of structure on drying and interfere with interparticle hydrogen binding as well as to enhance dispersement of particle structure in a continuous, polar phase such as water.
Although the mechanism by which maltodextrin and CMC act synergistically to keep the fibrils from bonding firmly together during drying has yet to be fully elucidated, it is believed to involve cooperative interaction, of sorts, between the two substances. The maltodextrin is believed to provide a glass-like matrix that encases the cellulose fibrils while the CMC apparently binds to the fibril surfaces sufficiently to retard collapse to the point that enough water is removed to solidify the entrapping matrix. The two substances in combination are very effective in prohibiting irreversible collapse of MDC during drying, thus allowing rapid dehydration and dispersement to occur and preserving to a substantial extent the favorable properties exhibited by never dried MDC.
The dispersion agent may optionally include lecithin in an amount from 0.1% to about 10% based on the weight of the MDC.
The following examples are provided to describe in further detail the preparation of MDC in accordance with the present invention. These examples are intended to illustrate and not to limit the invention.
EXAMPLE 1
Never dried white wheat fiber was mixed with 2,190 gallons of water in a hydrobeater (Black Clawson Model 4-SD-4 with Driver No. 45) to make up a pulp of 4.5% w/w solids, The white wheat fiber used in this example is a commercially available refined fiber product derived from bleached wheat chaff obtained from Watson Foods Company, West Haven Conn. The white wheat product was obtained as a nominal 40% w/w nonvolatile solids fiber mat. The product was stated to be 98% total dietary fiber by the Prosky method. The particle size by microscopic examination indicated a largely heterogeneous population of thin needle-like sclerchyma cells ranging in major/minor dimensions of 500 to 1000/10 to 20 microns with few interspersed parenchyma cells of 200/50 microns.
After beating the pulp for twenty minutes at room temperature it was transferred to a water jacketed holding tank to be repeatedly passed through a Black Clawson Twin Hydradisc refiner. The refiner of this example is a twenty-eight inch diameter double disc unit powered by a 250 horsepower motor. The refiner plates mounted on the discs are made of sharloy (a nickel hardened steel). The refiner plates were not equipped with dams. The faces of the particular refiner plates used in this refiner consists of alternate bars and grooves oriented so that bars of the adjacent refiner plates (one static and the other revolving) move relative to one another with a scissoring action occurring as the bars of each confronting plate move past one another. The three critical dimensions of these bars and grooves are the bar width, channel width and channel depth. For this particular unit, they were, respectively, 2/16 of an inch, 4/16 of an inch and 3/16 of an inch (expressed as 2,4,3 by Black Clawson's convention).
The refiner plates on the revolving disc move at 713 revolutions per minute. Based on the outer periphery of the refiner disc extending to 13 and 1/4 inches from the centerline of the drive shaft, this corresponds to peripheral speed of about 4,900 feet per minute. The pulp was continuously circulated at a rate of approximately 250 gallons per minute through the refiner and back to the holding tank. Passage of the cellulose suspension through the refiner occurs so as to have equal flow on each side of the revolving disc.
One disc of the refiner is fixed while the other is sliding. This allows the distance between adjacent discs to be adjusted. In the full open position (typical of startup or shutdown), discs are one and three-quarters inch apart. During refining, the discs are of the order of one to two thousands of an inch apart. Rather than adjust the gap between discs to a specific spacing, the value of the amperage to the motor driving the refiner is used to establish spacing. The procedure upon startup is to move the discs from the full open position to a closer position where the amperage reading increases until it reaches 310 amps. At this point, maximum power is being delivered from the motor. Once this point is reached, the back pressure on the refiner is increased by closing down the valve on the line returning pulp from the refiner to the holding tank. The back pressure is normally raised from an initial value of about 14 psig to a final value of about 35 psig. As the back pressure is increased without adjustment of the sliding disc location, the amperage drawn by the motor decreases to about 260 amps. With the back pressure at 35 psig, the sliding disc is adjusted to bring the discs closer together until the desired 310 amps are drawn by the motor. Once this is done, there is no further adjustment of the sliding disc unless the motor amperage drops significantly. This may occur as refining proceeds if certain properties of the pulp change significantly. In that event, the sliding disc is moved to reduce the gap between the discs until either the desired amperage is once again achieved, or the discs begin to squeal. Squealing is to be avoided as it is indicative of excessive disc wear and leads to high refiner plate replacement costs.
A gate-type mixer in the holding tank continuously mixed the contents during refining. A back pressure of 34 pounds per square inch was maintained in the return line from the refiner outlet to the holding tank. The recycle operation continued for approximately six hours during which the Canadian Standard Freeness of the pulp changed from an initial value of 190 to a final "false" value of 780 ml.
During refining the temperature of the pulp increased from an initial value of 64 to a final value of 190 degrees Fahrenheit. The amperage drawn by the 250 horsepower motor of the refiner varied from 310 initially to 290 amperes at completion of refining. Energy input to the refiner was approximately 1.2 kilowatt-hours per pound of refined fiber processed (dry weight basis).
The following examples illustrate the teachings of the invention.
EXAMPLE 2
A typical high alpha-cellulose content cellulose from wheat was refined to a Canadian Standard Freeness of 790 according to the procedure described in Example 1, above, mixed with dispersion agent and dried in a 25 square foot Buflovak double drum dryer (two 24-inch diameter, 24-inch width drums). The resultant mixture on a dry basis consisted of 56% w/w MDC, 39% w/w maltodextrin obtained from Staley, Decatur, IA (Lodex-15), 4% w/w carboxymethylcellulose type HP-5HS obtained from Dai-Ichikoyyo Seiyaku Company Ltd., Japan and 1% w/w soy lecithin obtained from Cargill, Decatur Ill. This mixture was then fed as an aqueous dispersion of 4.55% total solids at a rate of 414 pounds per hour to a double drum dryer to produce a dried product of 93.3% solids. The drums revolving at five revolutions per minute were heated by 100 psig steam. The nip thickness on both drums was set at 0.01 inches. Dried product was removed as a thin continuous film from the drums and subsequently ground to flake and powdered products.
Both the flake and powdered products were redispersed in water and the viscosity measured for comparison with the original MDC. All viscosities were measured in an aqueous dispersion at 1.5% w/w MDC solids and the additive concentrations noted above in a Brookfield Viscometer model DV-III with the small cell adapter using spindle SC4-16 at shear stresses imposed by a range of rotational speeds from 5 to 100 revolutions per minute (rpm). The viscosity of the aqueous dispersion of MDC with added dispersion agent before drying was 5,520 centipoise at 5 rpm. The 5 rpm viscosities of the dried flake and powdered products after drying and aqueous redispersion at the same solids content as the original dispersion with a Hamilton Beach Scovill Mixer model 936 ZSA at 2 minute (medium speed) were 3,410 and 3,095 centipoise, respectively. The complete viscosity/shear profiles for these three aqueous dispersions are shown in Table 1. The viscosity of the same powdered product after high shear redispersion for three minutes at 10,000 rpm with a Omni Digi-system rotostator type mixer (20 mm. generator) was 3,265 centipoise.
                                  TABLE 1                                 
__________________________________________________________________________
VISCOSITIES OF 1.5% W/W MDC AQUEOUS DISPERSIONS (cp)                      
Spindle RPM                                                               
        5  10 20 50  100                                                  
                        100                                               
                           50  20 10 5                                    
__________________________________________________________________________
Before Drying                                                             
        5520                                                              
           2990                                                           
              1940                                                        
                 1010                                                     
                     730                                                  
                        760                                               
                           1350                                           
                               2500                                       
                                  3600                                    
                                     5220                                 
From Flake                                                                
        3410                                                              
           2190                                                           
              1590                                                        
                 850 590                                                  
                        600                                               
                           920 1760                                       
                                  2570                                    
                                     3570                                 
From Powder                                                               
        3095                                                              
           1770                                                           
              1390                                                        
                 880 590                                                  
                        590                                               
                           900 1790                                       
                                  2530                                    
                                     3450                                 
__________________________________________________________________________
EXAMPLE 3
Never dried wheat fiber MDC refined to a false value of Canadian Standard Freeness of 780, according to the procedure described in Example 1, above, was mixed with dispersion agent and dried on a two foot wide by 100 foot long belt dryer. The resultant mixture on a dry basis consisted of 64.1% w/w MDC, 32.0% w/w maltodextrin, 3.2% w/w carboxymethylcellulose (CMC) and 0.7% w/w lecithin. The feed at a total solids content of 7.25% in an aqueous dispersion was fed at a rate of 917 pounds per hour to the dryer and dried to a solids content of 90% solids. The belt speed was 59 feet per minute and the nip thickness at the applicator bar was set at 0.026 inches. A sixty foot length of the belt was heated by 50 psig. steam. Dried product was removed as a thin continuous film and subsequently ground to flake and powdered products.
Film, flake and powdered products were redispersed in water and the viscosity measured for comparison with the original MDC as in EXAMPLE 1. The 5 rpm viscosity of the original MDC was 5,640 centipoise. The 5 rpm viscosities of the film, flake and powdered products after redispersion with a Hamilton Beach Mixer were 4,320, 3,775 and 3,410 centipoise, respectively. The viscosity/shear profiles for there four aqueous dispersions are set forth in Table 2.
              TABLE 2                                                     
______________________________________                                    
VISCOSITIES OF 1.5% W/W MDC AQUEOUS                                       
DISPERSIONS (cp)                                                          
Spindle RPM                                                               
          5      10    20  50  100  100  50  20  10  5                    
______________________________________                                    
Before Drying                                                             
          5640             580                                            
From Film 4320             605                                            
From Flake                                                                
          3775             595                                            
From Powder                                                               
          3410             580                                            
______________________________________                                    
While certain preferred embodiments of the present invention have been described and examplified above, it is not intended to limit the invention to such embodiments, but various modifications may be made thereto, without departing from the scope and spirit of the present invention as set forth in the following claims.

Claims (10)

What is claimed is:
1. A process for preparing dry, redispersible microdenominated cellulose comprising microdenominated cellulose prepared by repeatedly passing a liquid suspension of cellulose through a zone of high shear, said zone being defined by two confronting surfaces, with one of said surfaces rotating relative to the other, until said cellulose suspension is rendered substantially stable and has a Canadian Standard Freeness that consistently increases with repeated passage through said zone of high shear, said microdenominated cellulose having a settled volume of greater than 50% as determined on the basis of a 1.0% by weight suspension in water after twenty-four hours and drying said suspension of microdenominated cellulose in the presence of a dispersion agent in an amount effective to impart to said dry microdenominated cellulose a viscosity, when dispersed in water, of at least 50% of the viscosity of an equivalent concentration of never dried microdenominated cellulose dispersed in water.
2. A process according to claim 1 wherein said dispersion agent comprises maltodextrin and carboxymethylcellulose (CMC), the amount of said maltodextrin being about one-half to 1.5 times the weight of said microdenominated cellulose and the amount of said CMC being about of 5% to 15% of said weight of the microdenominated cellulose.
3. A process according to claim 1 wherein said suspension is dried as a substantially continuous film on a heated, moving belt dryer.
4. A process according to claim 1 wherein said suspension is dried as a substantially continuous film on a heated, double drum dryer.
5. A process according to claim 1 wherein lecithin is included in said dispersion agent in an amount from 0.1 to about 10% based on the weight of the microdenominated cellulose contained therein.
6. A composition comprising dry, microdenominated cellulose, said microdenominated cellulose being prepared by repeatedly passing a liquid suspension of fibrous cellulose through a zone of high shear, said zone being defined by two confronting surfaces, with one of said surfaces rotating relative to the other, until said cellulose suspension is rendered substantially stable and has a Canadian Standard Freeness that consistently increases with repeated passage through said zone of high shear, said microdenominated cellulose having a settled volume of greater than 50%, as determined on the basis of a 1.0% by weight suspension in water after twenty four hours and a water retention value greater than 500% and at least two dispersing agents, said dispersing agent consisting essentially of a first material selected from the group consisting of maltodextrins, complex polysaccharides, simple sugars and common edible disaccharides in an amount sufficient to form continuous encapsulating matrices on drying and a second material selected from the group consisting of CMC, locust bean gum, xanthan gum and guar gum in an amount sufficient to provide defloculating or repellant barriers between adjacent fibril surfaces, said amounts being effective to impart to said dry microdenominated cellulose a viscosity, when re-dispersed in water, of at least 50% of the viscosity of an equivalent concentration of never dried microdenominated cellulose dispersed in water.
7. A composition as claimed in claim 6, wherein said dispersing agent of the first type is maltodextrin and the dispersing agent of the second type is carboxymethylcellulose.
8. A composition according to claim 7 wherein the amount of said dispensing agent of the first type is in the range of about 50% to about 150% by weight of the microdenominated cellulose.
9. A composition according to claim 7 wherein the amount of said dispersing agent of the second type is in the range of about 5% to about 15% by weight of the microdenominated cellulose.
10. A composition comprising dry, microdenominated cellulose, said microdenominated cellulose being prepared by repeatedly passing a liquid suspension of fibrous cellulose through a zone of high shear, said zone being defined by two confronting surfaces, with one of said surfaces rotating relative to the other, until said cellulose suspension is rendered substantially stable and has a Canadian Standard Freeness that consistently increases with repeated passage through said zone of high shear, said microdenominated cellulose having a settled volume of greater than 50%, as determined on the basis of a 1.0% by weight suspension in water after twenty four hours and a water retention value greater than 500% and a dispersion agent comprising maltodextrin and carboxymethylcellulose (CMC), the amount of said maltodextrin being about one-half to 1.5 times the weight of said microdenominated cellulose and the amount of said CMC about 5% to 15% of the weight of the microdenominated cellulose.
US08/089,682 1993-07-09 1993-07-09 Redispersible microdenominated cellulose Expired - Lifetime US5487419A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US08/089,682 US5487419A (en) 1993-07-09 1993-07-09 Redispersible microdenominated cellulose
GB9500073A GB2296725B (en) 1993-07-09 1995-01-04 Cellulose compositions and their preparation
AU10029/95A AU692803B2 (en) 1993-07-09 1995-01-04 Redispersible microdenominated cellulose
FR9500097A FR2729160B1 (en) 1993-07-09 1995-01-06 DISPERSABLE MICRO-DIMENSIONED CELLULOSE
DE19500483A DE19500483B4 (en) 1993-07-09 1995-01-10 Redispersible micro-classified cellulose and process for its preparation

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US08/089,682 US5487419A (en) 1993-07-09 1993-07-09 Redispersible microdenominated cellulose
GB9500073A GB2296725B (en) 1993-07-09 1995-01-04 Cellulose compositions and their preparation
AU10029/95A AU692803B2 (en) 1993-07-09 1995-01-04 Redispersible microdenominated cellulose
FR9500097A FR2729160B1 (en) 1993-07-09 1995-01-06 DISPERSABLE MICRO-DIMENSIONED CELLULOSE
DE19500483A DE19500483B4 (en) 1993-07-09 1995-01-10 Redispersible micro-classified cellulose and process for its preparation

Publications (1)

Publication Number Publication Date
US5487419A true US5487419A (en) 1996-01-30

Family

ID=27506542

Family Applications (1)

Application Number Title Priority Date Filing Date
US08/089,682 Expired - Lifetime US5487419A (en) 1993-07-09 1993-07-09 Redispersible microdenominated cellulose

Country Status (5)

Country Link
US (1) US5487419A (en)
AU (1) AU692803B2 (en)
DE (1) DE19500483B4 (en)
FR (1) FR2729160B1 (en)
GB (1) GB2296725B (en)

Cited By (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2770091A1 (en) * 1997-10-29 1999-04-30 Rhone Poulenc Chimie Use of cellulose microfibrils as food additive
US6183596B1 (en) * 1995-04-07 2001-02-06 Tokushu Paper Mfg. Co., Ltd. Super microfibrillated cellulose, process for producing the same, and coated paper and tinted paper using the same
US6251222B1 (en) 1995-06-29 2001-06-26 Metsa-Serla Filler for use in paper manufacture and procedure for producing a filler
US6348436B1 (en) * 1996-07-15 2002-02-19 Rhodia Chimie Fluid comprising cellulose nanofibrils and its use for oil mining
US20030116289A1 (en) * 1999-11-03 2003-06-26 Regents Of The University Of Minnesota Cellulose fiber-based compositions and their method of manufacture
US20050129814A1 (en) * 2000-03-28 2005-06-16 Weibel Michael K. Method of producing edible cellulosic films
US20050223819A1 (en) * 2002-04-02 2005-10-13 Hans-Olof Backlund Method and a device for measuring stress forces in refiners
US20050271790A1 (en) * 2002-11-06 2005-12-08 Fiberstar, Inc. Reduced fat shortening, roll-in, and spreads using citrus fiber ingredients
US20060210687A1 (en) * 2002-11-06 2006-09-21 Fiberstar, Inc. Enhanced crackers, chips, wafers and unleavened using highly refined cellulose fiber ingredients
US20060222766A1 (en) * 2003-04-17 2006-10-05 Mueller Rolf Encapsulation system
US20060251789A1 (en) * 2002-11-06 2006-11-09 Fiberstar, Inc. Novel dairy product compositions using highly refined cellulosic fiber ingredients
US20080063755A1 (en) * 2006-09-13 2008-03-13 Renee Gan Baked Microwavable Frozen Bread and Bakery Products
US20080063758A1 (en) * 2006-09-13 2008-03-13 Christine Louise Kwiat Microwavable Food Products
US20080193590A1 (en) * 2002-11-06 2008-08-14 Fiberstar Inc., Incorporated Highly refined cellulose neutraceutical compostions and methods of use
US20090155419A1 (en) * 2006-09-13 2009-06-18 Renee Gan Microwavable Food Products
US20090155426A1 (en) * 2006-09-13 2009-06-18 Renee Gan Baked Microwavable Frozen Bread and Bakery Products
US20090269376A1 (en) * 2002-11-06 2009-10-29 Fiberstar, Inc. Stabilization of cosmetic compositions
WO2010092239A1 (en) 2009-02-13 2010-08-19 Upm-Kymmene Oyj A method for producing modified cellulose
WO2011116069A1 (en) * 2010-03-16 2011-09-22 North American Rescue, Llc Wound dressing
US20130000856A1 (en) * 2010-03-15 2013-01-03 Upm-Kymmene Oyj Method for improving the properties of a paper product and forming an additive component and the corresponding paper product and additive component and use of the additive component
CN104136681A (en) * 2012-02-13 2014-11-05 芬欧汇川集团 Method and apparatus for processing fibril cellulose and fibril cellulose product
US20140342075A1 (en) * 2011-09-14 2014-11-20 Nissei Company, Ltd. Frozen dessert and frozen dessert material
JP2018065920A (en) * 2016-10-19 2018-04-26 中越パルプ工業株式会社 Cellulose nanofiber and method for producing cellulose nanofiber
US10053817B2 (en) 2010-04-27 2018-08-21 Fiberlean Technologies Limited Process for the manufacture of structured materials using nano-fibrillar cellulose gels
US10294371B2 (en) 2009-03-30 2019-05-21 Fiberlean Technologies Limited Process for the production of nano-fibrillar cellulose gels
US10301774B2 (en) 2009-03-30 2019-05-28 Fiberlean Technologies Limited Process for the production of nano-fibrillar cellulose suspensions
US10577469B2 (en) 2015-10-14 2020-03-03 Fiberlean Technologies Limited 3D-formable sheet material
CN111587271A (en) * 2017-11-06 2020-08-25 克宁克莱克合作侨兴公司 Treatment of cellulose
US11155697B2 (en) 2010-04-27 2021-10-26 Fiberlean Technologies Limited Process for the production of gel-based composite materials
WO2021214300A1 (en) 2020-04-23 2021-10-28 Weidmann Holding Ag Composition comprising a fibrous material

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998033394A1 (en) 1997-01-31 1998-08-06 Fmc Corporation Texture and stabilizer composition

Citations (45)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US238044A (en) * 1881-02-22 luckenbach
US1631834A (en) * 1921-05-19 1927-06-07 Wood Conversion Co Gelatinizing wood
US2054301A (en) * 1935-04-17 1936-09-15 Brown Co Production of pulverulent cellulose
US2885154A (en) * 1954-08-17 1959-05-05 Texas Co Method of and apparatus for grinding solid materials by fluid energy
US3023104A (en) * 1960-07-05 1962-02-27 American Viscose Corp Food compositions incorporating cellulose crystallite aggregates
GB949464A (en) * 1959-09-23 1964-02-12 Neidl Georg Processing fibrous materials
US3186648A (en) * 1963-05-27 1965-06-01 Grace W R & Co Fluid energy mill
US3467317A (en) * 1966-09-26 1969-09-16 Fluid Energy Process Equip Fluid energy grinding method and means
US3643875A (en) * 1969-06-27 1972-02-22 Texaco Inc Fluid energy grinding method and system
US3701484A (en) * 1970-11-20 1972-10-31 Johns Manville Apparatus and process for suspending solids
GB1300820A (en) * 1969-10-24 1972-12-20 Mitsubishi Rayon Co Regenerated cellulose fibrous product and process for producing the same
US4087317A (en) * 1975-08-04 1978-05-02 Eucatex S.A. Industria E Comercio High yield, low cost cellulosic pulp and hydrated gels therefrom
US4143163A (en) * 1976-06-30 1979-03-06 Maxfibe, Inc. Coated fibrous cellulose product and process
US4173248A (en) * 1975-07-21 1979-11-06 Eucatex S.A. Industria E Comercio Medium density, high strength lignocellulose composition board including exhaustively hydrated cellulosic gel binder
US4216242A (en) * 1979-01-17 1980-08-05 Amiel Braverman Microcrystalline cellulose in freezable-gel-confection compositions
US4261521A (en) * 1980-03-13 1981-04-14 Ashbrook Clifford L Method and apparatus for reducing molecular agglomerate sizes in fluids
US4269859A (en) * 1979-04-19 1981-05-26 Brown Company Cellulose floc granules and process
US4336370A (en) * 1980-03-24 1982-06-22 International Paper Company Process for activating cellulose pulp to improve ease of esterification
US4341807A (en) * 1980-10-31 1982-07-27 International Telephone And Telegraph Corporation Food products containing microfibrillated cellulose
US4374702A (en) * 1979-12-26 1983-02-22 International Telephone And Telegraph Corporation Microfibrillated cellulose
US4378381A (en) * 1980-10-31 1983-03-29 International Telephone And Telegraph Corporation Suspensions containing microfibrillated cellulose
US4385172A (en) * 1980-03-24 1983-05-24 International Paper Company Prevention of hornification of dissolving pulp
US4452722A (en) * 1980-10-31 1984-06-05 International Telephone And Telegraph Corporation Suspensions containing microfibrillated cellulose
US4464287A (en) * 1980-10-31 1984-08-07 International Telephone And Telegraph Corporation Suspensions containing microfibrillated cellulose
US4481077A (en) * 1983-03-28 1984-11-06 International Telephone And Telegraph Corporation Process for preparing microfibrillated cellulose
US4481076A (en) * 1983-03-28 1984-11-06 International Telephone And Telegraph Corporation Redispersible microfibrillated cellulose
US4483743A (en) * 1981-10-22 1984-11-20 International Telephone And Telegraph Corporation Microfibrillated cellulose
US4487634A (en) * 1980-10-31 1984-12-11 International Telephone And Telegraph Corporation Suspensions containing microfibrillated cellulose
US4500546A (en) * 1980-10-31 1985-02-19 International Telephone And Telegraph Corporation Suspensions containing microfibrillated cellulose
US4533254A (en) * 1981-04-17 1985-08-06 Biotechnology Development Corporation Apparatus for forming emulsions
US4543410A (en) * 1982-06-21 1985-09-24 Morca, Inc. Absorbent cellulosic base structures
US4645606A (en) * 1985-04-24 1987-02-24 Ashbrook Clifford L Magnetic molecular agglomerate reducer and method
US4659388A (en) * 1984-06-08 1987-04-21 Daicel Chemical Industries, Ltd. Additive composition for foods or drugs
US4680189A (en) * 1986-07-07 1987-07-14 Warner-Lambert Company Ingestible, high density, compressed-tablet fiber-composition
US4692211A (en) * 1984-12-12 1987-09-08 Eucatex S.A. Industria E Comercio Of Sao Paulo High strength, cellulosic-gel-containing kraft paper and process for making the same
US4710390A (en) * 1986-07-07 1987-12-01 Warner-Lambert Company Ingestible, high density, compressed-tablet fruit fiber composition
US4761203A (en) * 1986-12-29 1988-08-02 The Buckeye Cellulose Corporation Process for making expanded fiber
US4764283A (en) * 1985-04-24 1988-08-16 Ashbrook Clifford L Method and apparatus for treating cooling tower water
US4780321A (en) * 1982-05-26 1988-10-25 Centre National De La Recherche Scientifique (Cnrs) Microcapsules having mixed walls formed of reticulated polyholosides and proteins and process for preparation thereof
US4863565A (en) * 1985-10-18 1989-09-05 Weyerhaeuser Company Sheeted products formed from reticulated microbial cellulose
US4908154A (en) * 1981-04-17 1990-03-13 Biotechnology Development Corporation Method of forming a microemulsion
US5026569A (en) * 1989-01-18 1991-06-25 The Procter & Gamble Company Cotton fiber particles for use in baked goods
US5073397A (en) * 1990-07-12 1991-12-17 Procter & Gamble Company Method for preparation of ultrafine citrus fiber and derivative fiber-enriched citrus beverages
WO1991019423A1 (en) * 1990-06-15 1991-12-26 Kraft General Foods, Inc. Polysaccharide hydrocolloid-containing food products
WO1991019421A1 (en) * 1989-06-15 1991-12-26 Kraft General Foods, Inc. Process for baked goods and products therefrom

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3573058A (en) * 1967-01-30 1971-03-30 Swift & Co Microcrystalline cellulose compositions co-dried with hydrocolloids
US3808090A (en) * 1970-10-01 1974-04-30 F Luhde Mechanical abrasion of wood particles in the presence of water and in an inert gaseous atmosphere
FR2331293A1 (en) * 1975-11-17 1977-06-10 Roquette Freres NEW APPLICATIONS OF THE POTATO PULP AND CORRESPONDING NEW PRODUCTS
DD127606A1 (en) * 1976-09-01 1977-10-05
JPS5455054A (en) * 1977-10-11 1979-05-01 Asahi Chem Ind Co Ltd Water-despersible compound
GB2066145B (en) * 1979-12-26 1983-05-25 Itt Microfibrillated cellulose
JPH0611793B2 (en) * 1989-08-17 1994-02-16 旭化成工業株式会社 Suspension of micronized cellulosic material and method for producing the same
JPH0598589A (en) * 1991-10-01 1993-04-20 Oji Paper Co Ltd Production of finely ground fibrous material from cellulose particle
US5385640A (en) * 1993-07-09 1995-01-31 Microcell, Inc. Process for making microdenominated cellulose

Patent Citations (45)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US238044A (en) * 1881-02-22 luckenbach
US1631834A (en) * 1921-05-19 1927-06-07 Wood Conversion Co Gelatinizing wood
US2054301A (en) * 1935-04-17 1936-09-15 Brown Co Production of pulverulent cellulose
US2885154A (en) * 1954-08-17 1959-05-05 Texas Co Method of and apparatus for grinding solid materials by fluid energy
GB949464A (en) * 1959-09-23 1964-02-12 Neidl Georg Processing fibrous materials
US3023104A (en) * 1960-07-05 1962-02-27 American Viscose Corp Food compositions incorporating cellulose crystallite aggregates
US3186648A (en) * 1963-05-27 1965-06-01 Grace W R & Co Fluid energy mill
US3467317A (en) * 1966-09-26 1969-09-16 Fluid Energy Process Equip Fluid energy grinding method and means
US3643875A (en) * 1969-06-27 1972-02-22 Texaco Inc Fluid energy grinding method and system
GB1300820A (en) * 1969-10-24 1972-12-20 Mitsubishi Rayon Co Regenerated cellulose fibrous product and process for producing the same
US3701484A (en) * 1970-11-20 1972-10-31 Johns Manville Apparatus and process for suspending solids
US4173248A (en) * 1975-07-21 1979-11-06 Eucatex S.A. Industria E Comercio Medium density, high strength lignocellulose composition board including exhaustively hydrated cellulosic gel binder
US4087317A (en) * 1975-08-04 1978-05-02 Eucatex S.A. Industria E Comercio High yield, low cost cellulosic pulp and hydrated gels therefrom
US4143163A (en) * 1976-06-30 1979-03-06 Maxfibe, Inc. Coated fibrous cellulose product and process
US4216242A (en) * 1979-01-17 1980-08-05 Amiel Braverman Microcrystalline cellulose in freezable-gel-confection compositions
US4269859A (en) * 1979-04-19 1981-05-26 Brown Company Cellulose floc granules and process
US4374702A (en) * 1979-12-26 1983-02-22 International Telephone And Telegraph Corporation Microfibrillated cellulose
US4261521A (en) * 1980-03-13 1981-04-14 Ashbrook Clifford L Method and apparatus for reducing molecular agglomerate sizes in fluids
US4385172A (en) * 1980-03-24 1983-05-24 International Paper Company Prevention of hornification of dissolving pulp
US4336370A (en) * 1980-03-24 1982-06-22 International Paper Company Process for activating cellulose pulp to improve ease of esterification
US4452722A (en) * 1980-10-31 1984-06-05 International Telephone And Telegraph Corporation Suspensions containing microfibrillated cellulose
US4487634A (en) * 1980-10-31 1984-12-11 International Telephone And Telegraph Corporation Suspensions containing microfibrillated cellulose
US4341807A (en) * 1980-10-31 1982-07-27 International Telephone And Telegraph Corporation Food products containing microfibrillated cellulose
US4464287A (en) * 1980-10-31 1984-08-07 International Telephone And Telegraph Corporation Suspensions containing microfibrillated cellulose
US4378381A (en) * 1980-10-31 1983-03-29 International Telephone And Telegraph Corporation Suspensions containing microfibrillated cellulose
US4500546A (en) * 1980-10-31 1985-02-19 International Telephone And Telegraph Corporation Suspensions containing microfibrillated cellulose
US4908154A (en) * 1981-04-17 1990-03-13 Biotechnology Development Corporation Method of forming a microemulsion
US4533254A (en) * 1981-04-17 1985-08-06 Biotechnology Development Corporation Apparatus for forming emulsions
US4483743A (en) * 1981-10-22 1984-11-20 International Telephone And Telegraph Corporation Microfibrillated cellulose
US4780321A (en) * 1982-05-26 1988-10-25 Centre National De La Recherche Scientifique (Cnrs) Microcapsules having mixed walls formed of reticulated polyholosides and proteins and process for preparation thereof
US4543410A (en) * 1982-06-21 1985-09-24 Morca, Inc. Absorbent cellulosic base structures
US4481076A (en) * 1983-03-28 1984-11-06 International Telephone And Telegraph Corporation Redispersible microfibrillated cellulose
US4481077A (en) * 1983-03-28 1984-11-06 International Telephone And Telegraph Corporation Process for preparing microfibrillated cellulose
US4659388A (en) * 1984-06-08 1987-04-21 Daicel Chemical Industries, Ltd. Additive composition for foods or drugs
US4692211A (en) * 1984-12-12 1987-09-08 Eucatex S.A. Industria E Comercio Of Sao Paulo High strength, cellulosic-gel-containing kraft paper and process for making the same
US4645606A (en) * 1985-04-24 1987-02-24 Ashbrook Clifford L Magnetic molecular agglomerate reducer and method
US4764283A (en) * 1985-04-24 1988-08-16 Ashbrook Clifford L Method and apparatus for treating cooling tower water
US4863565A (en) * 1985-10-18 1989-09-05 Weyerhaeuser Company Sheeted products formed from reticulated microbial cellulose
US4710390A (en) * 1986-07-07 1987-12-01 Warner-Lambert Company Ingestible, high density, compressed-tablet fruit fiber composition
US4680189A (en) * 1986-07-07 1987-07-14 Warner-Lambert Company Ingestible, high density, compressed-tablet fiber-composition
US4761203A (en) * 1986-12-29 1988-08-02 The Buckeye Cellulose Corporation Process for making expanded fiber
US5026569A (en) * 1989-01-18 1991-06-25 The Procter & Gamble Company Cotton fiber particles for use in baked goods
WO1991019421A1 (en) * 1989-06-15 1991-12-26 Kraft General Foods, Inc. Process for baked goods and products therefrom
WO1991019423A1 (en) * 1990-06-15 1991-12-26 Kraft General Foods, Inc. Polysaccharide hydrocolloid-containing food products
US5073397A (en) * 1990-07-12 1991-12-17 Procter & Gamble Company Method for preparation of ultrafine citrus fiber and derivative fiber-enriched citrus beverages

Cited By (56)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6183596B1 (en) * 1995-04-07 2001-02-06 Tokushu Paper Mfg. Co., Ltd. Super microfibrillated cellulose, process for producing the same, and coated paper and tinted paper using the same
US6214163B1 (en) 1995-04-07 2001-04-10 Tokushu Paper Mfg. Co., Ltd. Super microfibrillated cellulose, process for producing the same, and coated paper and tinted paper using the same
US6599391B2 (en) 1995-06-29 2003-07-29 M-Real Corporation Filler for use in paper manufacture and procedure for producing a filler
US6251222B1 (en) 1995-06-29 2001-06-26 Metsa-Serla Filler for use in paper manufacture and procedure for producing a filler
US6375794B2 (en) 1995-06-29 2002-04-23 Metsa-Serla Filler for use in paper manufacture and procedure for producing a filler
US6348436B1 (en) * 1996-07-15 2002-02-19 Rhodia Chimie Fluid comprising cellulose nanofibrils and its use for oil mining
WO1999021435A1 (en) * 1997-10-29 1999-05-06 Rhodia Chimie Use of cellulose microfibrils in dry form in food formulations
US6485767B1 (en) * 1997-10-29 2002-11-26 Rhodia Chimie Use of cellulose microfibrils in dry form in food formulations
FR2770091A1 (en) * 1997-10-29 1999-04-30 Rhone Poulenc Chimie Use of cellulose microfibrils as food additive
US7074300B2 (en) * 1999-11-03 2006-07-11 Regents Of The University Of Minnesota Cellulose fiber-based compositions and their method of manufacture
US7582213B2 (en) 1999-11-03 2009-09-01 Regents Of The University Of Minnesota Cellulose fiber-based filters
US20030116289A1 (en) * 1999-11-03 2003-06-26 Regents Of The University Of Minnesota Cellulose fiber-based compositions and their method of manufacture
US20060204631A1 (en) * 1999-11-03 2006-09-14 Regents Of The University Of Minnesota Cellulose fiber-based compositions and their method of manufacture
US6936291B1 (en) 2000-03-28 2005-08-30 Michael K. Weibel Method of producing edible cellulosic films
US7655165B2 (en) * 2000-03-28 2010-02-02 Weibel Michael K Method of producing edible cellulosic films
US20050129814A1 (en) * 2000-03-28 2005-06-16 Weibel Michael K. Method of producing edible cellulosic films
US20050223819A1 (en) * 2002-04-02 2005-10-13 Hans-Olof Backlund Method and a device for measuring stress forces in refiners
US20090269376A1 (en) * 2002-11-06 2009-10-29 Fiberstar, Inc. Stabilization of cosmetic compositions
US20050271790A1 (en) * 2002-11-06 2005-12-08 Fiberstar, Inc. Reduced fat shortening, roll-in, and spreads using citrus fiber ingredients
US8399040B2 (en) 2002-11-06 2013-03-19 Fiberstar Bio-Ingredient Technologies, Inc. Dairy product compositions using highly refined cellulosic fiber ingredients
US9629790B2 (en) 2002-11-06 2017-04-25 Fiberstar, Inc Stabilization of cosmetic compositions
US20080193590A1 (en) * 2002-11-06 2008-08-14 Fiberstar Inc., Incorporated Highly refined cellulose neutraceutical compostions and methods of use
US20060251789A1 (en) * 2002-11-06 2006-11-09 Fiberstar, Inc. Novel dairy product compositions using highly refined cellulosic fiber ingredients
US20060210687A1 (en) * 2002-11-06 2006-09-21 Fiberstar, Inc. Enhanced crackers, chips, wafers and unleavened using highly refined cellulose fiber ingredients
US20060222766A1 (en) * 2003-04-17 2006-10-05 Mueller Rolf Encapsulation system
US20090155426A1 (en) * 2006-09-13 2009-06-18 Renee Gan Baked Microwavable Frozen Bread and Bakery Products
US8354131B2 (en) 2006-09-13 2013-01-15 Kraft Foods Global Brands Llc Microwavable food products
US20090155419A1 (en) * 2006-09-13 2009-06-18 Renee Gan Microwavable Food Products
US20080063758A1 (en) * 2006-09-13 2008-03-13 Christine Louise Kwiat Microwavable Food Products
US8057832B2 (en) 2006-09-13 2011-11-15 Kraft Foods Global Brands Llc Microwavable food products
US20080063755A1 (en) * 2006-09-13 2008-03-13 Renee Gan Baked Microwavable Frozen Bread and Bakery Products
WO2010092239A1 (en) 2009-02-13 2010-08-19 Upm-Kymmene Oyj A method for producing modified cellulose
US9181653B2 (en) 2009-02-13 2015-11-10 Upm-Kymmene Oyj Method for producing modified cellulose
US10982387B2 (en) 2009-03-30 2021-04-20 Fiberlean Technologies Limited Process for the production of nano-fibrillar cellulose suspensions
US10294371B2 (en) 2009-03-30 2019-05-21 Fiberlean Technologies Limited Process for the production of nano-fibrillar cellulose gels
US10301774B2 (en) 2009-03-30 2019-05-28 Fiberlean Technologies Limited Process for the production of nano-fibrillar cellulose suspensions
US10975242B2 (en) 2009-03-30 2021-04-13 Fiberlean Technologies Limited Process for the production of nano-fibrillar cellulose gels
US20130000856A1 (en) * 2010-03-15 2013-01-03 Upm-Kymmene Oyj Method for improving the properties of a paper product and forming an additive component and the corresponding paper product and additive component and use of the additive component
WO2011116069A1 (en) * 2010-03-16 2011-09-22 North American Rescue, Llc Wound dressing
US10633796B2 (en) 2010-04-27 2020-04-28 Fiberlean Technologies Limited Process for the manufacture of structured materials using nano-fibrillar cellulose gels
US10100467B2 (en) 2010-04-27 2018-10-16 Fiberlean Technologies Limited Process for the manufacture of structured materials using nano-fibrillar cellulose gels
US11155697B2 (en) 2010-04-27 2021-10-26 Fiberlean Technologies Limited Process for the production of gel-based composite materials
US10053817B2 (en) 2010-04-27 2018-08-21 Fiberlean Technologies Limited Process for the manufacture of structured materials using nano-fibrillar cellulose gels
EP2756762A4 (en) * 2011-09-14 2015-08-05 Univ Kyoto Frozen dessert and frozen dessert raw material
US9271514B2 (en) * 2011-09-14 2016-03-01 Kyoto University Frozen dessert and frozen dessert material
US20140342075A1 (en) * 2011-09-14 2014-11-20 Nissei Company, Ltd. Frozen dessert and frozen dessert material
US9409998B2 (en) * 2012-02-13 2016-08-09 Upm-Kymmene Corporation Method and apparatus for processing fibril cellulose and fibril cellulose product
US20150045549A1 (en) * 2012-02-13 2015-02-12 Upm-Kymmene Corporation Method and apparatus for processing fibril cellulose and fibril cellulose product
CN104136681A (en) * 2012-02-13 2014-11-05 芬欧汇川集团 Method and apparatus for processing fibril cellulose and fibril cellulose product
US10577469B2 (en) 2015-10-14 2020-03-03 Fiberlean Technologies Limited 3D-formable sheet material
US11932740B2 (en) 2015-10-14 2024-03-19 Fiberlean Technologies Limited 3D-formable sheet material
US11384210B2 (en) 2015-10-14 2022-07-12 Fiberlean Technologies Limited 3-D formable sheet material
JP2018065920A (en) * 2016-10-19 2018-04-26 中越パルプ工業株式会社 Cellulose nanofiber and method for producing cellulose nanofiber
CN111587271A (en) * 2017-11-06 2020-08-25 克宁克莱克合作侨兴公司 Treatment of cellulose
CN111587271B (en) * 2017-11-06 2022-06-28 克宁克莱克合作侨兴公司 Treatment of cellulose
WO2021214300A1 (en) 2020-04-23 2021-10-28 Weidmann Holding Ag Composition comprising a fibrous material

Also Published As

Publication number Publication date
FR2729160A1 (en) 1996-07-12
DE19500483A1 (en) 1996-07-11
AU1002995A (en) 1996-07-11
GB2296725A (en) 1996-07-10
FR2729160B1 (en) 1997-04-04
GB2296725B (en) 1998-12-23
GB9500073D0 (en) 1995-03-01
DE19500483B4 (en) 2006-05-18
AU692803B2 (en) 1998-06-18

Similar Documents

Publication Publication Date Title
US5487419A (en) Redispersible microdenominated cellulose
US5385640A (en) Process for making microdenominated cellulose
FI95298C (en) A finely divided suspension of cellulosic material and a process for its preparation
EP2414435B1 (en) Process for the production of nano-fibrillar cellulose gels
EP2396470B1 (en) A method for producing modified cellulose
EP2917390B1 (en) Dry cellulose filaments and the method of making the same
DE3047351C2 (en)
EP2782937B1 (en) A method and a system for manufacturing cellulose material
CA2860811C (en) Method for concentrating fibril cellulose and fibril cellulose product
WO2001066600A1 (en) Stabilized microfibrillar cellulose
FI130254B (en) A process for producing microfibrillated cellulose and a product thereof
US20030116289A1 (en) Cellulose fiber-based compositions and their method of manufacture
JP2017527660A (en) Method for producing nanofibril cellulose
CA2139399C (en) Redispersible microdenominated cellulose
CH648071A5 (en) Micro-fibrillated cellulose and process for producing it
CA2139400A1 (en) Process for making microdenominated cellulose
JP4268574B2 (en) Method for producing high concentration fine cellulose fiber suspension
JPH0665417A (en) Fine particulate cellulosic raw material composition containing water
FI74309B (en) MICROFIBRILLATORS OF CELLULOSE AND FOUNDATION FOR FRAMSTAELLNING AV DENSAMMA.
CN115323819A (en) Method for improving nano-fibrillation efficiency of nano-cellulose

Legal Events

Date Code Title Description
STPP Information on status: patent application and granting procedure in general

Free format text: APPLICATION UNDERGOING PREEXAM PROCESSING

FEPP Fee payment procedure

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: SMALL ENTITY

AS Assignment

Owner name: MICROCELL, INC., CONNECTICUT

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:WEIBEL, MICHEL K.;REEL/FRAME:007688/0292

Effective date: 19930804

FPAY Fee payment

Year of fee payment: 4

FPAY Fee payment

Year of fee payment: 8

FPAY Fee payment

Year of fee payment: 12

AS Assignment

Owner name: WEIBEL, MICHAEL, CONNECTICUT

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:PAUL, RICHARD S.;REEL/FRAME:032367/0063

Effective date: 20140304

Owner name: WEIBEL, MICHAEL K., CONNECTICUT

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:MICROCELL, INC.;REEL/FRAME:032366/0662

Effective date: 20140305

Owner name: PAUL, RICHARD S., CONNECTICUT

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:MICROCELL, INC.;REEL/FRAME:032366/0662

Effective date: 20140305